Anthracene dye and process of making same.



BETTE Ti ifllfi FILIP-KACER, OF MANNHEIM, GERMANY, ASSIGNOR TO BADISOHE ANILIN & SODA FABRIK,

OF LUDWIGSHAFEN-ON-THE-RHINE, GERMANY, A CORPORATION.

ANTHB-ACENE DYE AND PROCESS OF MAKING- SAME.

Patented Aug. 17, 1909.

Application filed March 24, 1908. Serial No. 422,972.

of philosophy and chemist, subject of the King of Prussia, residing at Mannheim, Germany, iavemvented new and useful Improvements in Anthracene Dyes and Processes of-Making the Same, of which the following is a specification.

In the specification of application for British Letters Patent No. 16,7 /07 is described the production of a class of com-v pounds termed 2-methyl-anthrapyridon compounds.- I have now discovered that some of these 2--1nethyl-anthrapyridon compounds can also be employed in the production of new coloring matters, for instance 4- a1nino-2-methylanthrapyridon can be condensed with 2ehalogen-anthraquinone compoundssuchfor instance as Q-halOgen-anthraquinone itself, or with 2.6- or 2.7-.dihalo enanthraquinone, also i-halogen-Z -methy anthrapyridon, can be condensed with 2-aminoanthraquinone, or with 2.6- or 2.7-diaminoanthraqninone. If instead of first producing 4-halogen-2methylanthrapyridon and then condensing it with a .Z-aminoanthraquinone compound, 4 halogen 2 methyl 1-acetyl- 'aminoanthraquinone be condensed with the 2. amino anthraquinone compound, the same coloring matter results. In each case valuable red coloring .matter is obtained. That produced by condensing 4-amino-2 mcthyl-anthrapyridonwith 2-halogen-anthraquinone is-identical with the condensation' roduct of 4-halogen-2-inethylanthrapyri on with 2-amino-anthraquinone, in both cases the condensation is effected at the 4 position in the methylantlira )yridon body and in the 2 position in the ot ier anthraquinone residue, so that by these two difierent, but equivalent processes, the linking of the two anthraquinone groups at the said positions is effected. The other coloring matters possess similar properties. The reaction can be carried out by heating the compounds preferably in the presence of a condensing agent or, in order to neutralize the hydrochloric acid evolved, in the presence of sodium carbonate, or sodium acetate. It is also convenient to carry out the reaction in the presence of a solvent of a high boiling point, for instance, quinolin, and methyldiphenylamin, or a solvent of lower boiling point can be employed if the reaction be carried on under pressure.

My new coloring matters are insoluble in Water and in dilute acids and alkaliesand in alcohol and benzene, they are soluble 111 mtrobenzene and in quinoliu, and they yield violet solutions in concentrated sulfuric acld. They dye unmordanted cotton from a vat red.

The following examples will serve to illus-' trate further the nature of my invention and how it can be carried into practical effect, but my invention is not confined to these examples. The parts are by weight and the temperatures are in degrees centigrade.

Example 1: Boil together for from three (3), to four (4), hours in a reflux'apparatus, one hundred and fifty (150) parts of nitroben- Zene, ten (10) parts of -amidO-Q-metnyL-anthrapyridon (obtainable as described in the fourth example of the aforesaid British specification), eight and four-fifths (8.8) parts of 2-chlor-anthraquinone, ten (10) parts of anhydrous sodium acetate, and two (3) parts of cuprous chlorld. hen the mixture is cool, filter ofl the product and wash it consecutively with alcohol, water, dilute hydrochloric acid, and water. The product can be urified. by dissolving it in alkaline hydrosu fife solution, filtering the solution, and precipitatin the coloring mat ter by blowing air througn the filtrate.

EXample'Q: Boil together, in a reflux apparatus, one hundred and fifty (150) parts of nitrobenzene, ten (10) parts of 4-amino-2- methyl-anthrapyridon, live (5) parts of 2.6 ilichlor-anthraquinone, ten (10) parts of aiihydrous sodium acetate, and two (2) parts of on )LOUS chlorid. -Whcn the formation of the coloring matter is complete, work up as described in the foregoing first example. In this exam le the 2.(S-dichlor-anthraquinone can be rep aced by an equal quantity of 2.7- dichtor-anthraquinone.

Example 3: Heat together, in an autoclave, for ten (10) hours, at a temperature of from two hundred and thirty (230), to two hundred and forty (240) degrees, ten (10) arts of 4-chlor-2 methylanthrapyridon, eight (8) parts of 2-a1ninoanthraquinonc, fifteen (15) parts of sodium acetate, and one hundred and fifty (150) parts of .water.

Cir

hen the reaction product is cold, filter it 1 it in alkaline hydrosulfite solution, filtering I anthraquinon, two hundred and passing air through the filtrate.

Example 4: ,Boil together, ten (10) parts of 4-chlor-2-methyl-anthrapyridon, eight (8) parts of 2-aminoanthraqumone, ten (10) parts of anhydrous sodium acetate, and one undred (100) parts of quinolin. When the formation of the coloring matter is complete, allow the mixture to cool, filter o'fi' the coloring matter and wash it, first with alcohol and then with water.

. Example 5:- Heat together, in an auto-' clave, for ten (10) hours, at a temperature oftwo hundred and thirty (230), to two hundred and forty of 4-chlor-2-'methyl-anthrapyridon, four (4) parts of 2.6-diamino-anthraquinone, ten (10) parts of anhydrous sodium acetate, and fifty parts of phenol. When the reaction product is cold, dilute it with one hundred (100) parts of alcohol, filter off the coloring matter, and wash it with alcohol and water.

Example 6: Boil together, for from two (2), to three (3), hours, ten (10) parts of 4-chlor-2-methyl-anthra yridon, four (4) partsof 2.7-diamino-ant iraq'uinone, ten (10) arts of anhydrous sodium acetate, and one undred (100) parts of methyl-diphenylamin. When the reaction product is cold, filter off the coloring matter and wash it.

Example 7: Heat together, in an autoclave, for ten (10) hours, at a temperature of from two hundred and thirty (230), to two hundred and forty (240), degrees, four (4) parts of 4 chlor-2-methyl-l-aeetylamino-am thraquinone, three (3) parts of 2-aminoanthraquinone, four (4) parts of anhydrous sodium acetate, and twenty-five (25) parts of phenol. When the melt is cold, add about fifty (50) parts of alcohol, and filter off the coloring matter and then wash it with .alcohol and water. A

Example 8: Heat together, in an autoclave, for from eight (8), to ten (10), hours, at .a temperature of from two hundred and forty (240), to two-hundred and sixty (260), degrees, twenty (20) parts of 4c hlor-2- m ethyl-l-acetylaminoanthraquin'one, seven and three-fifths (7.6) parts of 2.6-diamino- (240), degrees, ten (10) parts.

' anthra 'oring matter being 2-methyl-anthra an equal weight of 2.7-di

and workup the meltasde- 5&-

process of producing coloring mat-" 2. The process of producing coloring mat ters of the anth'racene series by condensing ,4-halogen-2-methyl anthrapyridon with a 2 a'mino-anthraquinone.

- 3. The process of producing coloring matters of the anthracene series bycondensing '4 halogen 2 methyl-1-acetylamino anthraquinone with a Z-amino-anthraquinone.

4. The process of producing coloring niatters ofthe anthracene series by condensing 4 chlor- 2 -methyl-I-acetylamino anthraquinone witha.Z-amino-anthraquinone;-

5. As new articles oring matters being 2-methyl-anthra yridon uinone-amin compounds, w i'ch ar insolub e in water, and yield violet solutions in concentrated sulfuric acid and dye g re 1r danted cotton, from. a'. vat, yielding red shades. v

6. As a new article of manufacturethe colanthraquinone-amin -whieh 'i s inso uble in water. and in dilute acids and alkalies, and in alcohol and benzene, soluble in-nitrobenzene and quinolin, soluble in conc'entrated'sulfuric acidwith a violet color, and dyeing unmorrlanted i cotton from a vat, yielding red shades. v v

In testimony whereof I have hereunto set my hand in the witnesses.-

FILIP KACER. Witnesses:

J. Auto. LLOYD, Jos. H, LE TE.

of manufacture thecol-.

presence of two subscribing yridon- 

